Materials which can provide warm, patchouli-like, earthy, camphoraceous and woody fragrance notes are known in the art of perfumery. Many of the natural materials which provide such fragrances and contribute desired nuances to perfumery compositions are high in cost, vary in quality from one batch to another and/or are generally subject to the usual variations of natural products.
There is accordingly a continuing effort to find synthetic materials which will replace the essential fragrance notes provided by natural essential oils or compositions thereof. Unfortunately, many of these synthetic materials either have the desired nuances only to a relatively small degree or else contribute undesirable or unwanted odor to the compositions. The search for materials which can provide a more refined patchouli-like fragrance has been difficult and relatively costly in the areas of both natural products and synthetic products.
Buchi et al., 83 J.Am.Chem.Soc. 927 (1961), shows the production of a material called "patchoulione" which is stated to be octahydro-1,4,9,9-tetramethyl-3a,7-methanoazulen-5(4H)-one having the structure: ##STR2##
U.S. Pat. No. 3,748,284 issued on July 24, 1973 discloses perhydro derivatives of methanoazulen as having camphoraceous woody fragrances and having the ability to impart this fragrance to perfumed compositions and perfumed articles. The compounds disclosed are:
(a) Octahydro-1,4,9,9-tetramethyl-4,7-methanoazulen-3(2H)-one having the structure: ##STR3## (b) Octahydro-1,4,9,9-tetramethyl-4,7-methanoazulen-2(3H)-one having the structure: ##STR4## (c) Octahydro-1,4,9,9-tetramethyl-4,7-methanoazulen-8(7H)-one having the structure: ##STR5## PA1 2. German Offenlegungschrift No. 2,242,913 published Mar. 8, 1973 PA1 3. Dutch published Application No. 72/11760 published Mar. 5, 1973
Umarani et al., Sept./Oct. 1969, P. & E.O.R., 307 discloses two compounds relevant to the instant case: "isopatchoulinol" having the structure: ##STR6## and "patchouli alcohol" having the structure: ##STR7##
In addition, artificial flavoring agents for foodstuffs have received increasing attention in recent years. In many years, such food flavoring agents have been preferred over natural flavoring agents at least in part due to their diminished cost and their reproducible flavor qualities. For example, natural food flavoring agents such as extracts, concentrates and the like are often subject to wide variations due to changes in the quality, type and treatment of the raw materials. Such variations can be reflected in the end product and result in unfavorable flavor characteristics in said end product. Additionally, the presence of the natural product in the ultimate food may be undesirable because of increase tendency to spoil. This is particularly troublesome in food and food uses where such products as dips, soups, chips, sausages, gravies and the like are apt to be stored prior to use.
The fundamental problem in creating artificial flavor agents is that the artificial flavor to be achieved be as natural as possible. This generally proves to be a difficult task since the mechanism for flavor development in many foods is not completely known. This is noticeable in products having nutty, earthy, woody-balsamic, fresh walnut-kernel and walnut-skin flavor characteristics.
Reproduction of nutty, earthy, woody-balsamic, fresh walnut-kernel and walnut-skin flavor and aroma has been the subject of long and continuing searches by those engaged in a production of foodstuffs and beverages. The severe shortage of food in many parts of the world has given rise to the development of previously unused sources of protein which are unpalatable. Accordingly, the need has arisen for the use of flavoring materials which will make such sources of protein palatable to human sensory organs.
Even more desirable is a product that can serve to substitute for difficult-to-obtain natural perfumery oils and at the same time substitute for natural flavoring ingredients in both foodstuffs as well as in tobacco.
Mirrington and Schmalzl 37 J.Org.Chem. No. 18, 1972, pages 2871-2877 discloses the isolation of (-) patchouli alcohol having the structure: ##STR8## An article by Corey and Wipke entitled "Computer-Assisted Design of Complex Organic Syntheses" appearing in 166 Science 178 (1969) sets forth, interalia, the sequence of reactions leading to compounds having the structures: ##STR9## One of these reaction sequences involves performing the reactions: ##STR10## However, syntheses of lower methylene homologues and double compound isomers and an analogous patchouli alcohol and dihydropatchouli alcohol have not yet been disclosed in the prior art. Indeed, economic syntheses of patchouli alcohol itself do not appear to be given in the literature.
Danishevsky and Dumas 1968 Chemical Communication, Pages 1287-1288 discloses the synthesis of racemic patchouli alcohol and epi patchouli alcohol having the structure: ##STR11## by means of cyclization of a compound having the structure: ##STR12##
The use in perfumery of the compound having the structure: ##STR13## ("norpatchoulinol") is disclosed in the following patents: 1. Belgium Pat. No. 788,301 issued Mar. 1, 1973
A product of the reduction of this compound is also disclosed ("dihydro-norpatchoulinol"). This product has the structure: ##STR14## The compounds produced according to the process of the instant invention have properties considered to be unobvious, unexpected and advantageous with respect to the properties of the above-mentioned prior art compounds.
In addition, U.S. Pat. No. 3,879,466, issued on Apr. 22, 1975 and filed on Jan. 28, 1974 claims processes and compositions for altering the flavor and/or aroma of consumable products including foods, tobacco and perfumes utilizing as the essential ingredient at least one organic tricyclic alcohol having the formula: ##STR15## wherein each of R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 is selected from the group consisting of hydrogen and methyl; wherein the dashed line is a carbon-carbon single bond or a carbon-carbon double bond; wherein R.sub.1 is limited to hydrogen when (i) the dashed line is a carbon-carbon single bond; (ii) R.sub.2, R.sub.3, R.sub.4, R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 is hydrogen and (iii) R.sub.5 is hydrogen or methyl and wherein when the dashed line is a carbon-carbon single bond, one of R.sub.3 or R.sub.4 is hydrogen; and processes for preparing the above-mentioned compounds and in addition compounds having similar structures, that is, when the dashed line is either a carbon-carbon single bond or a carbon-carbon double bond; R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are each the same or different and each represents hydrogen and wherein when R.sub.3 or R.sub.4 is hydrogen the dashed line represents a carbon-carbon single bond and when R.sub.3 and R.sub.4 are both methyl, the dashed line represents a carbon-carbon double bond, involving first intimately admixing a methyl substituted cyclohexadienone having the structure: ##STR16## with an acetylenic compound having the structure: ##STR17## wherein X can be either hydroxyl, bromo or chloro thereby forming a diene compound having the structure: ##STR18## and then hydrogenating the diene compound with hydrogen in the presence of a hydrogenation catalyst thereby producing a ketone having the structure: ##STR19## It is further disclosed that this ketone may either be immediately cyclized using an alkali metal such as sodium, potassium or lithium in the case of X being halogen, or when X is OH, the ketone is first halogenated with a halogenating agent to first form a compound having the structure: ##STR20## wherein Y is bromo or chloro and subsequently the halogenated compound may then be cyclized using a cyclizing agent.
The compounds, uses and processes claimed in Ser. No. 436,848 filed on Jan. 28, 1974 do not contemplate the lower methylene homologues thereof of the instant case.
Furthermore, application for U.S. patent Ser. No. 436,847 filed on Jan. 28, 1974 claims chemical compounds having the structure: ##STR21## wherein Z is a moiety selected from the group consisting of: ##STR22## and wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, R.sub.9 and R.sub.10 are the same or different and each is selected from the group consisting of methyl and hydrogen and wherein R.sub.11 is selected from the group consisting of methyl, ethyl and hydrogen; and wherein X is selected from the group consisting of bromo, chloro, hydroxyl, benzyloxyl and alkoxyl and a process for preparing such compounds involving intimately admixing a methyl substituted cyclohexadienone having the structure: ##STR23## with one of the following acetylenic compounds having the structures: ##STR24## The generic process of U.S. Pat. No. 3,879,466, issued on Apr. 22, 1975 does not encompass the cyclization step of the process of the instant invention and is not specific to the compounds produced by the instant invention.